US5429862A - Biaxially oriented sealable polypropylene film having improved barrier properties - Google Patents
Biaxially oriented sealable polypropylene film having improved barrier properties Download PDFInfo
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- US5429862A US5429862A US08/154,030 US15403093A US5429862A US 5429862 A US5429862 A US 5429862A US 15403093 A US15403093 A US 15403093A US 5429862 A US5429862 A US 5429862A
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- US
- United States
- Prior art keywords
- sealable film
- film
- base layer
- weight
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 20
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 18
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 15
- 230000004888 barrier function Effects 0.000 title abstract description 9
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 20
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 15
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004711 α-olefin Substances 0.000 claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229920001897 terpolymer Polymers 0.000 claims abstract description 8
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 150000003505 terpenes Chemical class 0.000 claims description 9
- 235000007586 terpenes Nutrition 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000004760 silicates Chemical class 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000005022 packaging material Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 230000035699 permeability Effects 0.000 abstract description 7
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229930006739 camphene Natural products 0.000 description 1
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2813—Heat or solvent activated or sealable
- Y10T428/2817—Heat sealable
- Y10T428/2826—Synthetic resin or polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- the present invention relates to a multilayer polypropylene film which has been produced by coextrusion and which has improved barrier properties with respect to permeability to water vapor and oxygen and simultaneously possesses favorable slip properties and low shrink values, in order to ensure good machine running properties.
- the films disclosed therein possess, in particular, inadequate barrier properties towards water vapor, so that there has been a need for films having improved properties in this respect.
- DE-A-38 14 942 describes polypropylene films containing a resin proportion of 5 to 40% by weight in their base layers, the resins having a softening point in the range of 80° to 125° C. These films are used as shrink-on labels, but exhibit disadvantages with respect to the barrier properties towards water vapor and oxygen.
- Another object of the present invention is to provide a process for producing the improved film.
- a sealable film comprising (i) a base layer comprising polypropylene and a hydrocarbon resin having a softening point of at least 140° C. and (ii) at least one top layer comprising (a) an ethylene/propylene copolymer having an ethylene content of not more than about 10% by weight, (b) a propylene/1-butene copolymer, (c) a propylene/ethylene/alpha-olefin terpolymer, or (d) a blend of two or more of (a), (b) and (c), wherein said top layer contains an anti-blocking agent.
- the hydrocarbon resins has a softening point of less than 140° C., preferably from about 100° to 138° C.
- a process for producing the foregoing film comprising the steps of: producing by coextrusion through a slot die a cast film comprising said base layer and at least one said top layer; chilling said cast film on a chill roll; and then orienting said film by biaxial stretching in the longitudinal and transverse directions.
- a process for producing a multilayer sealable film comprising the step of incorporating in at least one layer of said film a resin having a softening point of at least 140° C. or less than 140° C.
- the films according to the present invention display reduced deposits on the rollers.
- the film of the instant invention is distinguished by improved processability, in particular with respect to machine running properties on high-speed packaging machines and to thermal blocking.
- machine running properties refers to the ease of processing on high-speed packaging machines.
- the film must be neither too smooth nor too rough, for this might cause jams during the slitting operation.
- the stiffness of a film is also important in this respect.
- thermal blocking relates to the mutual adhesion of film-packaged goods, which is, above all, caused by the action of heat. The lower this mutual adhesion between two adjoining film layers under the action of heat is, the better is the thermal blocking behavior.
- the films according to the present invention display reduced deposits on the rollers.
- the base layer preferably has a modulus of elasticity in the longitudinal direction of less than 3000 N/mm 2 , more preferably less than 2800 N/mm 2 , most preferably 2200 to 2800 N/mm 2 .
- the modulus of elasticity in the transverse direction is preferably less than 5200 N/mm 2 , more preferably in the range from 4000 to 5100 N/mm 2 .
- the modulus of elasticity is determined according to DIN 53,457 or ASTM-D 882, respectively.
- the low-molecular weight resin contained in the base layer is a natural or synthetic resin having a softening point of ⁇ 140° C. or a softening point of ⁇ 140° C., such as from 100° to 138° C., determined according to DIN 1995-U4, corresponding to ASTM E-28, and it is present in an amount of about 5 to 30% by weight, preferably of about 5 to 20% by weight, most preferably 5 to 10% by weight, relative to the total weight of the base layer.
- the barrier properties of the films towards water vapor are substantially improved, and that at the same time the optical properties and also the shrink behavior of the film are favorably influenced.
- the films according to this invention do not lead to deposits on rollers, e.g., during the longitudinal stretching. It has also been shown that as a result of their particular slip properties, the films of this invention are especially well-suited for use on high-speed packaging machines.
- the film surface is smooth enough to avoid so-called ⁇ slip-stick ⁇ effects, i.e., irregular running speeds. On the other hand, the roughness of the film surface is sufficiently high to avoid jams prior to the actual slitting operation.
- hydrocarbon resins in particular to the petroleum resins, styrene resins, cyclopentadiene resins and terpene resins (these resins are described in detail in ⁇ Ullmanns Enzyklopadie der Technischen Chemie ⁇ (Ullmann's Encyclopedia of Technical Chemistry), 4th edition, vol. 2, pp. 539-553).
- the term ⁇ petroleum resins ⁇ defines hydrocarbon resins produced by polymerization of deep-decomposed petroleum components in the presence of a catalyst.
- These petroleum materials usually contain a mixture of resin-forming substances, such as styrene, methylstyrene, vinyltoluene, indene, methylindene, butadiene, isoprene, piperylene and pentylene.
- the styrene resins are low-molecular weight styrene homopolymers or copolymers of styrene and other monomers, such as alpha-methylstyrene, vinyltoluene and butadiene.
- the cyclopentadiene resins are cyclopentadiene homopolymers or cyclopentadiene copolymers obtained from coal tar distillates and fractionated petroleum gas. The resins are produced by subjecting the cyclopentadiene-containing materials to high temperatures over a prolonged period of time. Depending on the reaction temperature, dimers, trimers or oligomers are obtained.
- the terpene resins include polymers of terpenes, i.e., hydrocarbons of the formula C 10 H 16 , which are present in practically all etherial oils or oil-containing vegetal resins, and also phenol-modified terpene resins.
- suitable terpenes include alpha-pinene, beta-pinene, dipentene, limonene, myrcene, camphene and similar terpenes.
- the hydrocarbon resins may also be chosen from among the so-called modified hydrocarbon resins. Modification is generally performed by reacting the raw materials prior to polymerization, by introducing special monomers or by reacting the polymerized product, whereby preference is given to hydrogenations or partial hydrogenations.
- Suitable hydrocarbon resins also include styrene homopolymers, styrene copolymers, cyclopentadiene homopolymers, cyclopentadiene copolymers and/or terpene polymers, which in each case have a softening point of ⁇ 140° C. (among the unsaturated polymers, preference is given to the hydrogenated products).
- the cyclopentadiene homopolymers having a softening point of ⁇ 140° C. are employed in the base layer.
- top layer(s), too, are to contain a hydrocarbon resin
- the resins listed above in the listed amounts for the base layer can be used.
- hydrocarbon resins having a softening point of ⁇ 140° C. such as between 100° C. and 183° C.
- suitable additives may be incorporated both in the base layer and in the top layer(s).
- Preferred additives include antistatic agents and/or antioxidants.
- the antioxidants employed preferably are so-called primary antioxidants, i.e., sterically hindered phenols or secondary amines, but it is also possible to use secondary antioxidants, such as, for example, thioethers or phosphites or phosphonites, or synergistic mixtures of primary and secondary anitoxidants.
- Secondary antioxidants such as, for example, thioethers or phosphites or phosphonites, or synergistic mixtures of primary and secondary anitoxidants.
- Antioxidants of this generic type are described, for example, in Gachter/Muller: Kunststoff-Additive (Plastics Additives), Carl Hanser Verlag, 2nd edition (1983). Below, the structural formulae of a number of suitable compounds are given: ##STR1##
- Preferred lubricants include carboxylic acid amides, such as erucic acid amide and stearic acid amide, or polydiorganylsiloxanes.
- Suitable anti-blocking agents include, for example, organic polymers which are incompatible with the raw material employed for the top layer(s), such as polyamides, polyesters, polycarbonates and the like, or inorganic substances such as silicates, silicon dioxide and calcium carbonate. Inorganic substances, in particular silicon dioxide, with an average particle size of 1 to 6 ⁇ m, have found to be most suitable. These anti-blocking agents are added in amounts of about 0.1 to 1% by weight, preferably of about 0.15 to 0.5% by weight, relative to the weight of the top layer(s).
- the thickness of the top layer(s) preferably varies between about 0.4 and 1.0 ⁇ m.
- the parameters for producing the films according to this invention are expediently selected such that stretching in the longitudinal direction is performed at a temperature between about 100° and 130° C., preferably between about 105° and 120° C., and at a stretch ratio between about 1:4 and 1:6. Stretching in the transverse direction is performed at a temperature between about 120° and 160° C., preferably between about 130° and 150° C. The stretching ratio in the transverse direction is higher than about 1:7.5, and preferably it is in the range of about 1:8 to 1:11. Following the stretching state in the transverse direction, the film is heat-set. During this treatment the film is conveyed in the tenter frame, optionally in a slightly converging manner, at a temperature which is about 5° to 50° C.
- a convergence range of about 5 to 15% is set for the heat-setting treatment.
- Ready printability of the film is achieved by subjecting the film to one of the conventional treatments prior to winding, such as, for example, to a flame treatment or electrical corona treatment.
- Corona treatment by means of any of the known methods is expediently performed such that the film is passed between two conductor elements which serve as electrodes, whereby a voltage which is high enough to cause spray or corona discharges is applied between the electrodes. This usually is an alternating voltage of about 10,000 V and a frequency of about 10,000 Hz.
- the air above the film is ionized and reacts with the molecules of the film surface, so that polar inclusions are obtained in the essentially non-polar polymer matrix.
- the treatment intensities are within the usual range; preferably they are between 38 and 42 mN/m.
- a three-layered, transparent film having a total thickness of 20 ⁇ m was produced by coextrusion and subsequent orientation by biaxial stretching.
- the film had the layer build-up ABA, ⁇ A ⁇ denoting the top layers and ⁇ B ⁇ denoting the base layer.
- Each of the top layers was 0.6 ⁇ m thick.
- the base layer was comprised of polypropylene to which 10% by weight of resin (ESCOREZ® ECR 356, supplied by Exxon, Darien, Conn., USA; softening point of the resin: 140° C.), relative to the total weight of the blend, had been added.
- the polypropylene had a melt flow viscosity of 3.5 g/10 min, determined according to DIN 53 735, under a load of 2.16 kg.
- the top layers were comprised of a propylene/ethylene copolymer having an ethylene content of 4.8% by weight, to which 0.8% by weight of polydimethylsiloxane, 0.13% by weight of a phenolic stabilizer (Antioxidant 330, supplied by Ethyl Corp., Brussels, Belgium, and Baton Rouge, La., USA), 0.075% by weight of calcium stearate and 0.33% by weight of SiO 2 having an average particle size of 2 ⁇ m, had been added.
- a phenolic stabilizer Antioxidant 330, supplied by Ethyl Corp., Brussels, Belgium, and Baton Rouge, La., USA
- the polydimethylsiloxane had a kinematic viscosity of 30,000 mm 2 /sec; the propylene/ethylene copolymer had a melt flow viscosity of 6.0 g/10 min, measured according to DIN 53 735, under a load of 2.16 kg.
- a film was produced as described in Example 1, except that the resin content of the base layer was 20% by weight (same resin as in Example 1).
- a film was produced as described in Example 1, except that the resin content of the base layer was 30% by weight (same resin as in Example 1).
- a film was produced as described in Example 2, except that the layer build-up was ABC.
- Top layer ⁇ A ⁇ had been corona-treated and did not contain any polydimethylsiloxane, whereas in top layer ⁇ C ⁇ the polydimethylsiloxane content had been doubled.
- Layer B was the base layer.
- Top layer ⁇ C ⁇ was comprised of a blend comprising an ethylene/propylene copolymer with an addition of 10% by weight of the resin employed in Example 1.
- a film was produced as described in Example 1 except that the resin was REGALITE® R101 (Hercules) having a softening point of 100° C.
- a film was produced as described in Example 1 except that the resin was REGALREZ® 1128 (Hercules) having a softening point of 130° C.
- a film was produced as described in Example 1, but without the addition of the resin.
- a film was produced as described in Example 1, except that a resin having a softening point of 85 ° C. was employed (ESCOREZ® 5380, supplied by Exxon).
- a film was produced as described in Example 2, except that no SiO 2 was contained in the top layers.
- two wooden blocks 72 mm ⁇ 41 mm ⁇ 13 mm
- the two blocks are wrapped into a sample of the film to be tested and sealed.
- the two blocks are stacked on top of one another, with the felt-clad surfaces facing each other, and loaded with a weight of 200 g.
- This arrangement is put in an oven preheated to 70° C. and left there for two hours. Then the temperature is reduced to room temperature (21° C.) for 30 minutes and the weight is lifted off from the wooden blocks.
- room temperature 21° C.
- the upper block is removed from the lower block. Evaluation is performed over the course of 4 individual measurements, from which the maximum take-down force (measured in N) is determined.
- the haze of the film is determined by a method similar to ASTM-D 1003-52, whereby a 1° slot aperture is used instead of the 4° round aperture, and the haze is indicated for four superimposed films, because in this way measurement can be performed within the optimum range. Haze is evaluated as follows:
- the gloss of the films is determined according to DIN 67 530.
- the reflector value is measured as an optical quantity for the surface of a film.
- the angle of radiation incidence is adjusted to 20°.
- a light beam hits the planar test surface at the set angle of incidence and is reflected or scattered by the test surface.
- the light beams incident on the photoelectronic receiver are indicated as a proportional electrical quantity.
- the measured value is dimensionless and must be given with the angle of incidence.
- the gloss (angle of incidence 20°) is evaluated using the following ratings:
- the modulus of elasticity is determined according to DIN 53,457 or ASTM-D 882.
- the shrink of a film is defined as the percental change in length (l o -l/l o ).
- Square film samples having a side length of 10 cm (l o ) are heated to a temperature of 120° C. for five minutes. Then the remaining length (1) is measured.
- the permeability to water vapor is determined in accordance with DIN 53 122, part 2.
- the barrier effect towards oxygen is measured according to draft standard DlN 53 380, part 3, at an atmospheric moisture content of 53%.
- the Table shows that with regard to the desired combination of properties, the films according to the present invention are superior to the films according to the Comparative Examples.
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- Laminated Bodies (AREA)
Abstract
Description
TABLE 1 __________________________________________________________________________ Shrink 120° C. O.sub.2 -Perm. 5 min in % Optical WVP (g/m.sup.2 · d) (cm.sup.3 /m.sup.2 · d · bar) longit./ Friction Thermal Properties Resin Depos. Machine Example in % in % transv. DIN 53375 Blocking (N) Haze/Gloss on Rollers Runnability __________________________________________________________________________ 1 0.88 1080 5/2 0.35 1 19/130 + ++ 2 0.79 770 7/3 0.35 1 18/125 + ++ 3 0.66 750 10/3 0.35 1 15/130 + ++ 4 0.79 770 7/3 0.35 1 19/125 + ++ 5 0.70 760 7/3 0.35 0.8 17/130 + ++ 6 0.93 1050 7/2 0.35 1 17/125 + ++ 7 0.95 1100 6/3 0.35 1 18/128 + ++ C1 1.40 1800 3/1 0.35 1 25/115 ++ ++ C2 0.85 1200 10/5 0.35 1 21/120 - ++ C3 0.79 1150 7/3 0.45 5 20/130 ++ - __________________________________________________________________________ WVP: Permeability to water vapor O.sub.2Perm.: Permeability to oxygen Friction: Determined according to DIN 53 375 Resin deposition on the rollers and machine runnability were evaluated by subjective visual inspection.
Claims (37)
Priority Applications (1)
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US08/154,030 US5429862A (en) | 1990-07-21 | 1993-11-18 | Biaxially oriented sealable polypropylene film having improved barrier properties |
Applications Claiming Priority (4)
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DE4023272.7 | 1990-07-21 | ||
DE4023272A DE4023272A1 (en) | 1990-07-21 | 1990-07-21 | BIAXIAL ORIENTED SEALABLE POLYPORPYLENE FILM WITH IMPROVED BARRIER PROPERTIES |
US73415791A | 1991-07-22 | 1991-07-22 | |
US08/154,030 US5429862A (en) | 1990-07-21 | 1993-11-18 | Biaxially oriented sealable polypropylene film having improved barrier properties |
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US73415791A Continuation-In-Part | 1990-07-21 | 1991-07-22 |
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US5429862A true US5429862A (en) | 1995-07-04 |
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US08/154,030 Expired - Lifetime US5429862A (en) | 1990-07-21 | 1993-11-18 | Biaxially oriented sealable polypropylene film having improved barrier properties |
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Cited By (13)
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US5595827A (en) * | 1993-07-16 | 1997-01-21 | Mitsui Petrochemical Industries, Ltd. | Polypropylene resin composition and the use of the same |
US5766532A (en) * | 1994-05-16 | 1998-06-16 | Hoechst Ag | Process for the production of a biaxially highly oriented polypropylene film |
US5910374A (en) * | 1992-09-18 | 1999-06-08 | Cryovac, Inc. | Moisture barrier film |
US6060139A (en) * | 1993-05-29 | 2000-05-09 | Hoechst Aktiengesellschaft | Resin-containing, biaxially oriented, multilayer polypropylene film, process for the production thereof, and the use thereof |
US6068936A (en) * | 1995-09-28 | 2000-05-30 | Ticona Gmbh | Polyolefin film containing cycloolefin polymer, process for the production thereof, and the use thereof |
WO2002068190A2 (en) * | 2001-02-22 | 2002-09-06 | Exxonmobil Oil Corporation | Multi-layer hermetically sealable film |
US6524720B1 (en) * | 1992-09-18 | 2003-02-25 | Cryovac, Inc. | Moisture barrier film |
US6528134B1 (en) | 2000-06-21 | 2003-03-04 | Pechiney Emballage Flexible Europe | Non-wax packaging film |
US20030211298A1 (en) * | 1999-12-30 | 2003-11-13 | Migliorini Robert A. | Multi-layer oriented polypropylene films with modified core |
EP1462246A1 (en) * | 2003-03-27 | 2004-09-29 | Futamura Kagaku Kogyo Kabushiki Kaisha | Biaxially oriented multilayer film |
US6855758B2 (en) * | 2000-09-29 | 2005-02-15 | Mitsubishi Polyester Film Gmbh | Hydrolysis-resistant, transparent, biaxially oriented film made from a crystallizable thermoplastic, and process for its production |
US20090042023A1 (en) * | 2004-12-27 | 2009-02-12 | Aldo Arruda Mortara | Heat-Sealable Bi-Oriented Polypropylene Film, Use of this Film and an Article Prepared from Said Film |
US20100260996A1 (en) * | 2009-04-10 | 2010-10-14 | Dow Global Technologies Inc. | High performance sealable coextruded biaxially oriented polypropylene film |
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US5910374A (en) * | 1992-09-18 | 1999-06-08 | Cryovac, Inc. | Moisture barrier film |
US6579621B1 (en) | 1992-09-18 | 2003-06-17 | Cryovac, Inc. | Moisture barrier film |
US6524720B1 (en) * | 1992-09-18 | 2003-02-25 | Cryovac, Inc. | Moisture barrier film |
US6060139A (en) * | 1993-05-29 | 2000-05-09 | Hoechst Aktiengesellschaft | Resin-containing, biaxially oriented, multilayer polypropylene film, process for the production thereof, and the use thereof |
US5595827A (en) * | 1993-07-16 | 1997-01-21 | Mitsui Petrochemical Industries, Ltd. | Polypropylene resin composition and the use of the same |
US5766532A (en) * | 1994-05-16 | 1998-06-16 | Hoechst Ag | Process for the production of a biaxially highly oriented polypropylene film |
US6068936A (en) * | 1995-09-28 | 2000-05-30 | Ticona Gmbh | Polyolefin film containing cycloolefin polymer, process for the production thereof, and the use thereof |
US20030211298A1 (en) * | 1999-12-30 | 2003-11-13 | Migliorini Robert A. | Multi-layer oriented polypropylene films with modified core |
US6528134B1 (en) | 2000-06-21 | 2003-03-04 | Pechiney Emballage Flexible Europe | Non-wax packaging film |
US6855758B2 (en) * | 2000-09-29 | 2005-02-15 | Mitsubishi Polyester Film Gmbh | Hydrolysis-resistant, transparent, biaxially oriented film made from a crystallizable thermoplastic, and process for its production |
WO2002068190A3 (en) * | 2001-02-22 | 2003-02-06 | Exxonmobil Oil Corp | Multi-layer hermetically sealable film |
WO2002068190A2 (en) * | 2001-02-22 | 2002-09-06 | Exxonmobil Oil Corporation | Multi-layer hermetically sealable film |
EP1462246A1 (en) * | 2003-03-27 | 2004-09-29 | Futamura Kagaku Kogyo Kabushiki Kaisha | Biaxially oriented multilayer film |
US20040191551A1 (en) * | 2003-03-27 | 2004-09-30 | Kentaro Ishii | Biaxially oriented multilayer film |
US20090042023A1 (en) * | 2004-12-27 | 2009-02-12 | Aldo Arruda Mortara | Heat-Sealable Bi-Oriented Polypropylene Film, Use of this Film and an Article Prepared from Said Film |
US20100260996A1 (en) * | 2009-04-10 | 2010-10-14 | Dow Global Technologies Inc. | High performance sealable coextruded biaxially oriented polypropylene film |
US8609228B2 (en) | 2009-04-10 | 2013-12-17 | Dow Global Technologies Llc | High performance sealable coextruded biaxially oriented polypropylene film |
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